Electropolishing

The need for defect-free, flat silicon surfaces led to the first investigations in this field, which were performed as early as 1958 [Tul]. It was found that electropolishing of silicon is possible in HF if the applied anodic potential is sufficient to produce current densities in excess of the critical value JPS. 

Electropolishing under galvanostatic conditions can be used to remove bulk silicon in a well-defined manner. This can for example be used to profile doping density or diffusion length versus the thickness of the sample, as discussed in Sections 10.2 and 10.3. The thickness D of the removed silicon layer can be calculated from the applied current density J, the anodization time t, the dissolution valence nv, the atomic density of silicon Nsi and the elementary charge e. 

As shown in Fig. 4.5, the dissolution valence n., shows a relatively constant value of 4 for electropolishing current densities well above JPS and a bias below 10 V. 

Si(111) surfaces after (a) immersion in aque- followed by electrochemical hydrogenation 

For higher bias oxygen evolution is observed in some cases, which leads to values of tty in excess of 4. 

Ionic liquid is acting as an electrolyte. Specific benefits of the ionic liquid are  

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Under diffusion-controlled dissolution conditions (in the anodic direction) the crystal orientation has no influence on the reaction rate as only the mass transport conditions in the solution detennine the process. In other words, the material is removed unifonnly and electropolishing of the surface takes place. 

Zirconium is readily attacked by acidic solutions containing fluorides. As Httle as 3 ppm flouride ion in 50% boiling sulfuric acid corrodes zirconium at 1.25 mm/yr. Solutions of ammonium hydrogen fluoride or potassium hydrogen fluoride have been used for pickling and electropolishing zirconium. Commercial pickling is conducted with nitric—hydrofluoric acid mixtures (see Metal surface treatments). 

In the early days of TEM, sample preparation was divided into two categories, one for thin films and one for bulk materials. Thin-films, particularly metal layers, were often deposited on substrates and later removed by some sort of technique involving dissolution of the substrate. Bulk materials were cut and polished into thin slabs, which were then either electropolished (metals) or ion-milled (ceramics). The latter technique uses a focused ion beam (typically Ar+) of high-energy, which sputters the surface of the thinned slab. These techniques produce so-called plan-view thin foils. 

See Figures I0-93A and I0-93B as limited examples of reaction and other process vessels that require heat transfer for proper processing. Markovitz reports improved heat transfer for the inside of jacketed vessels when the surface has been electropolished, which gives a fine, bright surface. 

In uniform corrosion the superficial or geometrical area of the metal is used to evaluate both the anodic and cathodic current density, although it might appear to be more logical to take half of that area. However, surfaces are seldom smooth and the true surface area may be twice to three times that of the geometrical area (a cleaved crystal face or an electropolished single crystal would have a true surface area that approximates to its superficial area). It follows, therefore, that the true current density is smaller than the superficial current density, but whether the area used for calculating /, and... 

Electropolishing appears to be helpful in reducing the tendency of pits to develop at surface imperfections, but not necessarily at sites associated with structural features of the metal. 

Uranium tarnishes readily in the atmosphere at room temperature. Electropolishing inhibits the process whilst etching in nitric acid activates the surface. Uranium dioxide and hydrated UO3 are the principal solid products. 

The presence of hydrogen in pre-exposed specimens was revealed by straining specimens in vacuo. Hydrogen evolution occurred in the elastic region of the stress/strain curve, an effect that had been shown to be very much reduced by electropolishing pre-exposed specimens prior to testing... 

The enormous scope of the subject of corrosion follows from the definition which has been adopted in the present work. Corrosion will include all reactions at a metal/environment interface irrespective of whether the reaction is beneficial or detrimental to the metal concerned —no distinction is made between chemical or electropolishing of a metal in an acid and the adventitious deterioration of metal plant by acid attack. It follows, therefore, that a comprehensive work on the subject of corrosion should include an account of batteries, electrorefining, chemical machining, chemical and electrochemical polishing, etc. 

Electropolishing which exploits a generally similar type of solution, but introduces anodic currents as an additional means of dissolution thereby providing better control of rapid processing. Electrosmoothing and electrobrightening are terms used to describe inferior finishes which may have lustre but have lower specular reflectivity. 

Electropolishing techniques utilise anodic potentials and currents to aid dissolution and passivation and thus to promote the polishing process in solutions akin to those used in chemical polishing. The solutions have the same basic constitution with three mechanistic requirements—oxidant (A), contaminater (B) and diffusion layer promoter (C) —but, by using anodic currents, less concentrated acid solutions can be used and an additional variable for process flexibility and control is available. 

The simplest and most thoroughly studied solutions are those based on phosphoric acid at low temperatures (<35°C) which alone can fulfil all three requirements of acid solvent, film former (as metal phosphate) and diffusion agent by virtue of its viscosity. Thus copper and its main alloys of brasses and bronzes can be very effectively electropolished in 60-70% orthophos-phoric acid with the temperature maintained below 35°C under other conditions copper passivates or dissolves freely under mass transfer controlled conditions, but by varying the conditions appropriately polishing can be continued under mild agitation. An annotated polarisation curve is given in Fig. 11.7 readers are referred to recent studies for more detailed 2ispects " . 

Only copper can be electropolished in such a simple solution, but by minor modification other metals can be treated. Such modifications include (a) increasing the acidity, or (b) increasing the oxidant level for aluminium, iron and steel, nickel alloys etc ... 

Fig. 11.7 Annotated anodic polarisation curve for the electropolishing of copper in...

The solutions cease to electropolish well once they contain substantial amounts of metal or when the potential is incorrectly set the departure from good finishing is recognised by the development of etch or pit features, often at edges or recesses, and this led Hoar to express the critical... 

A very substantial literature may now be found for electropolishing solution formulation and Table 11.5 gives some of the well-established compositions and operating conditions. Further solutions may be found in the standard reference books and for specialist applications and metals... 

Electropolishing surface finishing of a metal by making it the anode in an appropriate solution, whereby a bright and level surface showing specular reflectivity is obtained. 

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